Reliable measurements of interfacial slip by colloid probe atomic force microscopy. III. Shear-rate-dependent slip

We present experimental evidence and theoretical models that demonstrate that the slip length, which is the departure from the hydrodynamic no-slip boundary condition, cannot be constant as commonly assumed, but must decrease with increasing shear rate to avoid an unphysical divergence in the velocity of the fluid adjacent to the surface at small separations. The molecular origin of the shear rate dependence of the slip length is discussed. A new theoretical model for slip (the saturation model) is obtained, and it is shown to describe accurately colloid probe atomic force microscopy force measurements for all separations down to a few nanometers in two partially wetting situations (di-n-octyl phthalate on silanized silicon and bare silicon). Previous observations of slip length increasing with shear rate are explained as due to an imprecise calculation of the drag force on the cantilever. A new way of plotting experimental data is also presented, which provides a useful way to illustrate the slip length dependence on the shear rate.     

Reliable measurements of interfacial slip by colloid probe atomic force microscopy. II. Hydrodynamic force measurements

Here we report a new study on the boundary conditions for the flow of a simple liquid in a confined geometry obtained by measuring hydrodynamic drainage forces with colloid probe atomic force microscopy (AFM). In this work, we provide experimental data obtained using a best practice experimental protocol and fitted with a new theoretical calculation (Zhu, L.; Attard, P.; Neto, C. Langmuir 2010, submitted for publication, preceding paper). We investigated the hydrodynamic forces acting on a silica colloid probe approaching a hydrophobized silicon surface in a single-component viscous Newtonian liquid (di-n-octylphthalate), a partially wetting system. The measured average slip lengths were in the range of 24-31 nm at approach velocities of between 10 and 80 μm/s. Using our experimental approach, the presence of nanoparticle contaminants in the system can be indentified, which is important because it has been shown that nanoparticles lead to a large apparent slip length. Under our stringent control of experimental conditions, the measurement of the slip length is reproducible and independent of the spring constant of the cantilever.     

Analysis of bacterial adhesion using a gradient force analysis method and colloid probe atomic force microscopy

The atomic force microscope (AFM) has been used to examine the stickiness of bacteria on the basis of the analysis of approach and retraction force curves between the AFM tip and the bacterial surface. One difficulty in analyzing approach curve data is that the distance between the AFM tip and the surface of the bacterium is difficult to define. The exact distances are difficult to determine because the surface of the bacterium deforms during force imaging, producing a highly nonlinear region in the approach curve. In this study, AFM approach and retraction curves were obtained using a colloid probe AFM for three strains of Escherichia coli (D21, D21f2, and JM109). These strains differed in their relative adhesion to glass surfaces, on the basis of measurements of sticking coefficients in packed bed flow through column tests. A gradient force curve analysis method was developed to model the interactions between the colloid probe and a surface. Gradient analysis of the approach curve revealed four different regions of colloid-surface interactions during the approach and contact of the probe with the bacterial surface: a noninteraction region, a noncontact phase, a contact phase, and a constant compliance region. The noncontact phase, which ranged from 28 to 59 nm for the three bacterial strains, was hypothesized to arise primarily from steric repulsion of the colloid by extracellular polymers on the bacterial surface. The contact phase, spanning 59-113 nm, was believed to arise from the initial pressure of the colloid on the outer membrane of the cell. The constant compliance region likely reflected the response of the colloid probe to the stiff peptidoglycan layer that confers strength and rigidity to gram negative bacteria. It was shown that the sticking coefficients reported for the three E. coli strains were correlated with the length of the noncontact phase but not the properties of the other phases. Sticking coefficients were also not correlated with any parameters determined from retraction force curves such as pull-off distances or separation energies. These results show that gradient analysis is useful for studying the contribution of the length of the exopolymers on the cell surface to bacterial adhesion to glass surfaces.     

Pull-off force measurements between rough surfaces by atomic force microscopy

Direct measurements of the pull-off (adhesion) forces between pharmaceutical particles (beclomethasone dipropionate, a peptide-type material, and lactose) with irregular geometry and rough polymeric surfaces (series of polypropylene coatings, polycarbonate, and acrylonitrile-butadiene-styrene) were carried out using the atomic force microscope. These measurements showed that roughness of the interacting surfaces is the significant factor affecting experimentally measured pull-off forces. A broad distribution of pull-off force values was noted in the measurements, caused by a varying adhesive contact area for a particle located on rough substrate. The possibility of multiple points of contact between irregularly shaped pharmaceutical particles and substrate surfaces is demonstrated with nanoindentations of the particle in a fluoro-polymer film. Force-distance curves showing the "sawtooth" pattern are additional evidence that particles make contact with substrates at more than one point. Reduced adhesion of 10- to 14-microm-diameter lactose and peptide material particles to the polypropylene coatings with a roughness of 194 nm was found in this study. Similar pull-off force versus roughness relationships are also reported for the model spherical particles, silanized glass particle with a size of 10 microm and polystyrene particle with a diameter of 9 microm, in contact with polypropylene coatings of varying roughness characteristics. It was found that the model recently proposed by Rabinovich et al. (J. Colloid Interface Sci. 232, 1-16 (2000)) closely predicts the pull-off forces for glass and lactose particles. On the other hand, the adhesion of the peptide material and polystyrene particle to polypropylene is underestimated by about an order of magnitude with the theoretical model, in which the interacting substrates are treated as rigid materials. The underestimate is attributed to the deformation of the peptide material and polystyrene particles.     

Young's moduli of surface-bound liposomes by atomic force microscopy force measurements

Mechanical properties of layers of intact liposomes attached by specific interactions on solid surfaces were studied by atomic force microscopy (AFM) force measurements. Force-distance measurements using colloidal probe tips were obtained over liposome layers and used to calculate Young's moduli by using the Hertz contact theory. A classical Hertz model and a modified Hertz one have been used to extract Young's moduli from AFM force curves. The modified model, proposed by Dimitriadis, is correcting for the finite sample thickness since Hertz's classical model is assuming that the sample is infinitely thick. Values for Young's moduli of 40 and 8 kPa have been obtained using the Hertz model for one and three layers of intact liposomes, respectively. Young's moduli of approximately 3 kPa have been obtained using the corrected Hertz model for both one and three layers of surface-bound liposomes. Compression work performed by the colloidal probe to compress these liposome layers has also been calculated.     

Adhesion forces between functionalized latex microspheres and protein-coated surfaces evaluated using colloid probe atomic force microscopy

Proteins are important in bacterial adhesion, but interactions at molecular-scales between proteins and specific functional groups are not well understood. The adhesion forces between four proteins [bovine serum albumin (BSA), protein A, lysozyme, and poly-d-lysine] and COOH, NH2 and OH-functionalized (latex) colloids were examined using colloid probe atomic force microscopy (AFM) as the function of colloid residence time (T) and solution ionic strength (IS). For three of the proteins, OH-functionalized colloids produced higher adhesion forces to proteins (2.6-30.5 nN; IS=1 mM, T=10s) than COOH- and NH2-functionalized colloids (1.6-6.8 nN). However, protein A produced the largest adhesion force (8.1+/-1.0 nN, T=10 s) with the COOH-functionalized colloid, demonstrating the importance of specific and unanticipated protein-functional group interactions. The NH2-functionalized colloid typically produced the lowest adhesion forces with all proteins, likely due to repulsive electrostatic forces and weak bonds for NH2-NH2 interactions. The adhesion force (F) between functionalized colloids and proteins consistently increased with residence time (T), and data was well fitted by F=ATn. The constant value of n=0.21+/-0.07 for all combinations of proteins and functionalized colloids indicated that water exclusion and protein rearrangement were the primary factors affecting adhesion over time. Adhesion forces decreased inversely with IS for all functional groups interacting with surface proteins, consistent with previous findings. These results demonstrate the importance of specific molecular-scale interactions between functional groups and proteins that will help us to better understand factors colloidal adhesion to surfaces.     

Direct measurement of interactions between stimulation-responsive drug delivery vehicles and artificial mucin layers by colloid probe atomic force microscopy

A novel thermo- and pH-sensitive nanogel particle, which is a core-shell structured particle with a poly(N-isopropylacrylamide) (p(NIPAAm)) hydrogel core and a poly(ethylene glycol) monomethacrylate grafted poly(methacrylic acid) (p(MMA-g-EG)) shell, is of interest as a vehicle for the controlled release of peptide drugs. The interactions between such nanogel particles and artificial mucin layers during both approach and separation were successfully measured by using colloid probe atomic force microscopy (AFM) under various compression forces, scan velocities, and pH values. While the magnitudes of the compression forces and scan velocities did not affect the interactions during the approach process, the adhesive force during the separation process increased with these parameters. The pH values significantly influenced the interactions between the nanogel particles and a mucin layer. A large steric repulsive force and a long-range adhesive force were measured at neutral pH due to the swollen p(MMA-g-EG) shell. On the other hand, at low pH values, the steric repulsive force disappeared and a short-range adhesive force was detected, which resulted from the collapse of the shell layer. The nanogel particles possessed a pH response that was sufficient to protect the incorporated peptide drug under the harsh acidic conditions in the stomach and to effectively adhere to the mucin layer of the small intestine, where the pH is neutral. The relationships among the nanogel particle-mucin layer interactions, pH conditions, scan velocities, and compression forces were systemically investigated and discussed.     

Isoelectric point of fluorite by direct force measurements using atomic force microscopy

Interaction forces between a fluorite (CaF2) surface and colloidal silica were measured by atomic force microscopy (AFM) in 1 x 10(-3) M NaNO3 at different pH values. Forces between the silica colloid and fluorite flat were measured at a range of pH values above the isoelectric point (IEP) of silica so that the forces were mainly controlled by the fluorite surface charge. In this way, the IEP of the fluorite surface was deduced from AFM force curves at pH approximately 9.2. Experimental force versus separation distance curves were in good agreement with theoretical predictions based on long-range electrostatic interactions, allowing the potential of the fluorite surface to be estimated from the experimental force curves. AFM-deduced surface potentials were generally lower than the published zeta potentials obtained from electrokinetic methods for powdered samples. Differences in methodology, orientation of the fluorite, surface carbonation, and equilibration time all could have contributed to this difference.     

Impact of atomic force microscopy on interface and colloid science

Since its invention twenty years ago the atomic force microscope (AFM) has become one of the most important tools in colloid and interface science. The reason for this impact is that the AFM allows doing experiments on length, time, force, and energy scales, which are not accessible by any other technique. These experiments can be carried out under natural conditions, for example in liquid environments. In this paper we specify the length and time scales involved, give examples where by using the AFM relevant questions in colloid and interface science have been solved, and we discuss future perspectives.     

Fabrication and characterization of metal-molecule-metal junctions by conducting probe atomic force microscopy

Metal-molecule-metal junctions were fabricated by contacting Au-supported alkyl or benzyl thiol self-assembled monolayers (SAMs) with an Au-coated atomic force microscope (AFM) tip. The tip-SAM microcontact is approximately 15 nm(2), meaning the junction contains approximately 75 molecules. Current-voltage (I-V) characteristics of these junctions were probed as a function of SAM thickness and load applied to the microcontact. The measurements showed: (1) the I-V traces were linear over +/-0.3 V, (2) the junction resistance increased exponentially with alkyl chain length, (3) the junction resistance decreased with increasing load and showed two distinct power law scaling regimes, (4) resistances were a factor of 10 lower for junctions based on benzyl thiol SAMs compared to hexyl thiol SAMs having the same thickness, and (5) the junctions sustained fields up to 2 x 10(7) V/cm before breakdown. I-V characteristics determined for bilayer junctions involving alkane thiol-coated tips in contact with alkane thiol SAMs on Au also showed linear I-Vs over +/-0.3 V and the same exponential dependence on thickness. The I-V behavior and the exponential dependence of resistance on alkyl chain length are consistent with coherent, nonresonant electron tunneling across the SAM. The calculated conductance decay constant (beta) is 1.2 per methylene unit ( approximately 1.1 A(-)(1)) for both monolayer and bilayer junctions, in keeping with previous scanning tunneling microscope and electrochemical measurements of electron transfer through SAMs. These measurements show that conducting probe-AFM is a reliable method for fundamental studies of electron transfer through small numbers of molecules. The ability to vary the load on the microcontact is a unique characteristic of these junctions and opens opportunities for exploring electron transfer as a function of molecular deformation.     

Application of colloid probe atomic force microscopy to the adhesion of thin films of viscous and viscoelastic silicone fluids

The adhesive characteristics of thin films (0.2-2 μm) of linear poly(dimethylsiloxane) (PDMS) liquids with a wide range of molecular weights have been measured using an atomic force microscope with a colloid probe (diameters 5 and 12 μm) for different separation velocities. The data were consistent with a residual film in the contact region having a thickness of ～6 nm following an extended dwell time before separation of the probe. It was possible to estimate the maximum adhesive force as a function of the capillary number, Ca, by applying existing theoretical models based on capillary interactions and viscous flow except at large values of Ca in the case of viscoelastic fluids, for which it was necessary to develop a nonlinear viscoelastic model. The compliance of the atomic force microscope colloid beam was an important factor in governing the retraction velocity of the probe and therefore the value of the adhesive force, but the inertia of the beam and viscoelastic stress overshoot effects were not significant in the range of separation velocities investigated.     

Combined atomic force microscopy and fluorescence correlation spectroscopy measurements to study the dynamical structure of interfacial fluids

We have studied the dynamic structure of thin (approximately a few nanometers) liquid films of a nearly spherical, nonpolar molecule tetrakis(2-ethylhexoxy)silane (TEHOS) by using a combination of atomic force microscopy (AFM) and fluorescence correlation spectroscopy (FCS). Ultra-sensitive interferometer-based AFM was used to determine the stiffness (force gradient) and the damping coefficient of the liquid film. The experiments show oscillations in the damping coefficient with a period of approximately 1 nm, which is consistent with the molecular dimension of TEHOS as well as previous X-ray reflectivity measurements. Additionally, we performed FCS experiments for direct determination of the molecular dynamics within the liquid film. From the fluctuation autocorrelation curve, we measured the translational diffusion of the probe molecule embedded within the fluid film formed on a solid substrate. The autocorrelation function was best fitted with two components, which indicate that the dynamics are heterogeneous in nature. However, the heterogeneity is not as pronounced as had been previously observed for molecularly thin liquid films sandwiched between two solid substrates.     

Atomic force microscopy reveals hydroxyapatite-citrate interfacial structure at the atomic level

An approach to organic-inorganic interfacial structure at the atomic level is a great challenge in the studies of biomineralization. We demonstrate that atomic force microscopy (AFM) is powerful tool to discover the biomineral interface in detail. By using a model system of (100) hydroxyapatite (HAP) face and citrate, it reveals experimentally that only a side carboxylate and a surface calcium ion are involved in the binding effect during the citrate adsorption, which is against the previous understandings by using Langmuir adsorption and computer simulation. Furthermore, the adsorbed citrate molecules can use their free carboxylate and hydroxyl groups to be self-assembled on the HAP surface. AFM examination also finds that the presence of citrate molecules on the HAP crystal faces can enhance the adhesion force of the HAP surface. We suggest that the established AFM method can be used for a precise and direct understanding of biointerfaces at the atomic level.     

Interaction forces between metal-chelating lipid monolayers measured by colloidal probe atomic force microscopy

Surface forces between LB films of metal-chelating lipids in water have been studied using colloidal probe atomic force microscopy. The LB films of an amphiphile functionalized by the iminodiacetic acid group were prepared on hydrophobic glass substrates. The electric double layer repulsion operated between these LB film surfaces changed depending on pH reflecting the different protonation states of the iminodiacetic acid groups. The titration curve of the iminodiacetic acid monolayer was obtained from the force profiles. The Cu²⁺ complexation process was also monitored by measuring the force profiles at various Cu²⁺ ion concentrations.     

Characterization of distance-dependent damping in tapping-mode atomic force microscopy force measurements in liquid

We have used a spectral analysis method to characterize changes in the local damping coefficient for an acoustically driven cantilever as it approaches a hard surface in liquid. We show a significant distance dependence of the damping coefficient (and associated quality factor) that must be accounted for to achieve successful theoretical reproduction of experimental tapping-mode force curves. We model the cantilever dynamics using a forced damped harmonic oscillator model and solve the equation of motion using the method of finite differences. Experiments in solutions of differing viscosities show that bulk viscous damping is not the source of the system dissipation, while simulations of the cantilever dynamics including adhesion hysteresis also eliminate this as the origin of the dissipation. We conclude that frictional dissipation that occurs with the intermittent contact is the likely source of dissipation in the system. Our results identify a semiquantitative means of interpreting tapping-mode force curves on nondeformable surfaces in liquid.     

Molecular views and measurements of hemostatic processes using atomic force microscopy

Hemostasis and thrombosis are highly complex and coordinated interfacial responses to vascular injury. In recent years, atomic force microscopy (AFM) has proven to be a very useful approach for studying hemostatic processes under near physiologic conditions. In this report, we review recent progress in the use of AFM for studying hemostatic processes, including molecular level visualization of plasma proteins, protein aggregation and multimer assembly, and structural and morphological details of vascular cells under aqueous conditions. AFM offers opportunities for visualizing surface-dependent molecular and cellular interactions in three dimensions on a nanoscale and for sensitive, picoNewton level, measurements of intermolecular forces. AFM has been used to obtain molecular and sub-molecular, resolution of many biological molecules and assemblies, including coagulation proteins and cell surfaces. Surface-dependent molecular processes including protein adsorption, conformational changes, and subsequent interactions with cellular components have been described. This review outlines the basic principles and utility of AFM for imaging and force measurements, and offers objective perspectives on both the advantages and disadvantages. We focus primarily on molecular level events related to hemostasis and thrombosis, particularly coagulation proteins, and blood platelets, but also explore the use of AFM in force measurements and surface property mapping.     

Single molecule charging by atomic force microscopy

AFM/KPM charging and charge mapping of polyamine charge carriers in a PMMA matrix is reported. Selective charging of the designed charge carrier is demonstrated at concentrations down to a single molecule. This works constitutes electrochemical charging and detection of single redox-active organic molecules in low dielectric matrices by probe microscopy.     

Measuring molecular weight by atomic force microscopy

Absolute-molecular-weight distribution of cylindrical brush molecules were determined using a combination of the Langmuir Blodget (LB) technique and Atomic Force Microscopy (AFM). The LB technique gives mass density of a monolayer, i.e., mass per unit area, whereas visualization of individual molecules by AFM enables accurate measurements of the molecular density, i.e., number of molecules per unit area. From the ratio of the mass density to the molecular density, one can determine the absolute value for the number average molecular weight. Assuming that the structure of brush molecules is uniform along the backbone, the length distribution should be virtually identical to the molecular weight distribution. Although we used only brush molecules for demonstration purpose, this approach can be applied for a large variety of molecular and colloidal species that can be visualized by a microscopic technique.